Integrated process for the production of biofuels from different types of starting materials and related products

ABSTRACT

Process for the production of biocombustible or biofuel mixtures suitable for different conditions of use, starting from refined or raw vegetable oils, including those extracted from seaweed, and/or from used food oils and animal fats, each of which is pre-treated with specific treatments in order to yield a dried refined oil. The latter then undergoes transesterification with an excess of lower alcohols or bioalcohols, and a subsequent separation into a raw glycerine-based phase and a phase containing mixtures of fatty acid alkyl esters and the excess alcohols or bioalcohols.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a National Stage entry of International ApplicationNo. PCT/IT2007/000490, filed Jul. 6, 2007, the entire specificationclaims and drawings of which are incorporated herewith by reference.

The present invention concerns an integrated process for the productionof biofuels and biocombustibles from different types of startingmaterials and the related products. More specifically, the inventionconcerns a process yielding new biofuel mixtures from the treatment ofrefined or raw vegetable oils, including those extracted from algaeand/or microalgae, either seaweed or other varieties, produced inaquaculture or in thermal bioreactors, and from the treatment of animalfats and used frying oils, as well as through feeding calibratedproportions of alcohols or bioalcohols of low molecular weight into theoil-based mixture in order to obtain combustible products and ecologicalfuels suitable for the various environmental conditions and for thekinds of systems or engines they must be used in.

As is known, the demand for renewable, ecologically compatible energy isincreasingly more pressing in view of the gradual reduction of fossilfuel reserves and of the environmental risks represented by increasingatmospheric pollution and the greenhouse effect. This is why the studyand development of fuels and combustibles of biological origin hasconsiderably increased over the last few decades. Two of the mostwidespread and consolidated methods for producing energy starting frombiomass are bioethanol and biodiesel production.

In general, biomass means any organic substance or material directly orindirectly deriving from chlorophyll photosynthesis. Through thisprocess, plants take in water and carbon dioxide from their environmentand, through the sun's energy and the nutrients present in the soil, thewater and carbon dioxide are then turned into organic material usefulfor the plant's growth. From a production standpoint, the most importanttypes of biomass are forestry residues, waste products from the timberand papermaking industry, waste of zootechnics enterprises and municipalsolid waste, but also vegetable materials coming from specificcultivations such as sugar beet and sugarcane, cereals and their wasteproducts, algae and/or microalgae, aquaculture and/or in thermalbioreactors, and oleaginous seeds of plants such as soy, colza andsunflower. It is evident that, if the materials produced either directlyor indirectly from these agricultural activities are used for energyapplications involving combustion, then, on the one hand, the energygenerated will not affect fossil fuel reserves and, on the other, thecarbon dioxide produced in this combustion will be compensated, in theoverall energy balance, by the carbon dioxide consumed by the relativeplant of origin via the chlorophyll synthesis.

Bioethanol is produced by the anaerobic fermentation of biomassescontaining sugars and/or starches, such as various cereals and theirwaste products, various wastes of agrofood processing and cultivations,and sugarcane and sugar beet production. Specifically, sugarcane isgrown deliberately for the production of bioethanol for motor vehicles.This is particularly found in Brazil, where ethyl alcohol is the mainsource of fuel commonly used in internal combustion engines. Also inEurope, bioethanol has been taken into consideration as a possiblepetrol substitute, even if its energy yield is lower than that of petroland a complete substitution would call for the use of specially designedengines. According to current European Union legislation, bioethanolmust be used in an amount of 1% in a mixture with petrol. Thispercentage is destined to rise to 5% and requires making no changes toexisting engines. Moreover, in some countries like France and Spain,ethyl tertiary butyl ether (ETBE), a tertiary butyl ether derived frombioethanol, is currently used in a 15% mix with petrol. Finally, innorthern European countries like Sweden there are already newly designedcars circulating that are fuelled by an 85% bioethanol and 15% petrolmixture.

Biodiesel is instead meant to replace diesel fuel in motor vehicles andheating systems, and is obtained from widespread purposely grownoleaginous plants like colza and sunflower. Other starting materialsinclude soy, maize, cotton, coconut, palm seed or linseed oils or evenoils deriving from marine or other algae and/or microalgae eitherproduced in aquaculture or in thermal bioreactors, or spent food oilssuch as used frying oils, and animal fats. The oils contained in theseproducts (generally known as “combustible vegetable oil” or “purevegetable oil”) are triglycerides of fatty acids in which the fatty acidalcohol chains linked to the glycerine molecule normally contain 12-18carbon atoms. Owing to their high viscosity, these products must betreated in order to break down the triglyceride molecules into threeseparate molecules, derived from fatty acids, and into a glycerinemolecule. In effect, the treatment replaces the glycerine triester withthree monoesters of a lower alcohol, normally methanol or ethanol,according to the following reaction, where R, R′ and R″ representsaturated or unsaturated alcohol chains, normally with 12-22 carbonatoms, and, in the case shown, the alcohol replacing glycerine ismethanol.

There are three basic ways to produce alkyl esters for biofuels startingfrom oils and fats of biological origin (biolipids):

-   -   direct base-catalysed transesterification of the biolipid.    -   direct acid-catalysed transesterification of the biolipid.    -   conversion of the biolipid first into fatty acids and then into        lower alkyl esters.

Transesterification, which is practically an alcoholysis of thetriglyceride by means of a short-chain monofunctional alcohol, mainlymethanol or ethanol, is the most convenient transformation method. Inparticular, base-catalysed transesterification (with a homogeneouscatalyst, that is, in solution in the reaction mixture) is the cheapestand currently most widespread process. It normally requires temperaturesin the region of 70-130° C. and pressures of 1-1.5 bar, with aconversion yield of about 85%.

The biodiesel produced by transesterification from combustible vegetableoil thus consists of a mixture of alkyl esters, particularly methyl orethyl esters, of fatty acids and has a more homogeneous overallcomposition than that of fossil diesel fuel; it also has greaterbiodegradability and greater oxygen content because each moleculecontains an ester function, —O—CO—.

As will be clearer below, biodiesel use, if compared to fossil fuel use,enables a reduction in the gaseous emissions of engines that areconsidered dangerous for health. Moreover, as already noted, this useallows to bring to zero the balance of the carbon dioxide produced,thereby contributing to limiting the overall greenhouse effect in theatmosphere. This is because the CO₂ produced in the combustion of acertain amount of biodiesel quantitatively corresponds to the amountused in the photosynthesis in the cultures for the production ofvegetable oils destined for biofuels.

According to current European legislation, biodiesel is used in amountsof 1% in a mixture with conventional diesel fuel for motor vehicles, butthese amounts should shortly reach and exceed 5%. Larger amounts, even30%, are already used in certain vehicles, such as in public transportbuses. In this case, too, using up to about 30% of biodiesel in dieselengines does not need any particular technical modifications, while morerecently designed engines can even be fuelled by 100% pure biodiesel.

The older biodiesel production plants using combustible vegetable oilsas starting material are besed on processes in batch. They generally useonly one kind of starting material and the transesterification processtakes place in a single phase. As already noted, in traditionalproduction plants, transesterification takes place at a relatively hightemperature (such as 130° C.) and there is a limited recovery of thecatalyst, and a methanol recovery only in the final phase of theprocess. Particular care is necessary to monitor the quantity of waterand free fatty acids in the starting biolipid. If the level of freefatty acids or humidity is too high, there may be processes ofsaponification and glycerine separation at the end of the process.

With traditional processing plants, the final product obtained is amixture of methyl esters with a high humidity and glycerine content: theglycerine obtained as a by-product has a purity ranging between 75% and80%.

Processing plants of more recent construction operate in a continuousmode and at a lower temperature (around 70° C.), and in this case thetransesterification takes place in several stages, with recovery of bothmethanol and ethanol, which can be recycled in the process. Toaccelerate the process, besides using suitable catalysts enhancing thespeed and efficiency of the reaction, excess alcohol is used (normally1:6, expressed in moles, that is, double the stoichiometric ratio) andthe glycerine formed is eliminated.

The alcohol in the alkyl ester solution can be separated bydistillation, while a small part remains in the aqueous solution, fromwhich it can also be extracted.

An example of the continuous process for producing alkyl esters (inparticular, methyl esters) of fatty acids deriving from vegetable oilsand using homogeneous catalysis techniques with soluble bases ascatalysts, such as sodium hydroxide and sodium methylate, and in whichthe reaction is carried out in at least two consecutive stages, isdescribed in European patent EP 0523767 (Metallgesellschaft AG).

The fuel of biological origin which is currently referred to asbiodiesel, which has been briefly described above, does not havesuitable characteristics for certain final uses, including use at lowtemperatures. This is the case, for example, with aeronauticalapplications, where engines must be able to run at temperatures in theregion of −70° C.

As is known, turbine engines are used both in energy production and inthe aeronautical industry. Their positive features consist of theirquick start-up of plants and thus the immediate availability of power,as well as good functional reliability. On the other hand, they entailconsiderable energy consumption and pollution, especially at maximumpower levels. In the aeronautical case, the maximum power requirement ofan aircraft is when taking off and landing, and this adds to airpollution.

For their characteristics, turbine power stations should be activatedonly to cover peak energy consumption times and emergencies, but incountries where demands for energy exceeds the availability, these powerstations are used for very long periods.

Both as regards use in aviation and in power stations, besides reducingfuel consumption, it would be extremely advantageous to have fuels thatcan reduce pollutants emissions, and this is why also in these fieldsthe availability of suitable fuels or combustibles of biological originis extremely important. The possibility of diluting normal aircraft fuelwith a biocompatible product of a biodiesel type, but which can becalibrated to obtain the functional characteristics suitable for use inextreme conditions as those of aircraft engines, would meet importantcriteria of economy and environmental protection in this field.

In view of the above, an object of the present invention is to provide aproduction process to obtain biofuel mixtures that can, on the one hand,be extremely flexible as regards supply of raw materials, being suitableto process any material based on animal or vegetable oil or fatincluding waste matter of food processing and used frying oils, while,on the other hand, offering the same high flexibility as regards thecharacteristics of usability of the resulting product. In particular,such product must be able to withstand the same conditions as any normalbiodiesel, either in a pure state or diluted with established amounts offossil fuel, but it must also be available for use—in more suitablequantities and proportions of its components—as fuel or as a diluent ofconventional fuels, in extreme conditions, and particularly at lowtemperatures, or in situations where the extreme purity of emissions isa critical requirement.

To this end, the present invention proposes a process essentially basedon the transesterification of vegetable oils of various origin, both rawand refined oils, of biolipids of animal origin or even lipid-basedwaste products of food processing, such as used frying oils. Beforeundergoing the transesterification process, these materials are suitablypre-treated according to the kind of starting material and its origin,and then suitably dried in order to provide a dried refined oil that isas consistent and reproducible as possible for the transesterificationprocess. Downstream of transesterification, in the process proposedaccording to the present invention, the lower alcohol that is used inexcess for transesterification can be completely separated from thereaction mixture and recovered, or it can be recovered in part, or mayeven be fed into the final mixture with a quantity of additionalalcohol, of the same or different type, in order to obtain—in the finalproduct—a calibrated quantity of one or more different lower alcohols ina mixture with the fatty acid alkyl esters resulting from thetransesterification process.

The new product resulting from the aforesaid process is syntheticallycalled “Bio-oil” to distinguish it (both in terms of intrinsicconstitution and performance) from conventional biodiesel.

Thus, the present invention specifically provides a process for theproduction

of biocombustible and biofuel mixtures suitable for different conditionsof use, comprising the following fundamental operations:

-   -   a) producing mixtures of fatty acid alkyl esters and glycerine        by transesterification, starting from lipid-based vegetable or        animal materials and from lower alcohols or bioalcohols in        excess;    -   b) separating the mixtures deriving from the said operation a)        of transesterification into a phase based on raw glycerine and a        phase containing the said mixtures of fatty acid alkyl esters        and the excess amount of lower alcohols or bioalcohols;        characterised by the fact that the said starting lipid-based        vegetable or animal materials include one or more of the        following ingredients:

i. raw vegetable oil

ii. refined vegetable oil

iii. used food oil and/or animal fats

and by the fact that the said ingredients undergo the followingpreliminary treatments upstream of said operation a) oftransesterification:

-   -   1) the said ingredient i), raw vegetable oil, is subjected to a        preliminary depuration and refining treatment in order to remove        impurities and to neutralise and winterize it, and then to        drying of the refined oil thus obtained;    -   2) the said ingredient ii), refined vegetable oil, is subjected        to preliminary drying;    -   3) the said ingredient iii), used food oil and/or animal fats,        is subjected to a preliminary depuration treatment, to drying        and then to an esterification of the free fatty acids contained        therein, by addition of lower alcohols or bioalcohols; the        obtained product based on fatty acid alkyl esters is mixed in a        proportion of not more than 20% with dried refined oil obtained        from treatments 1) or 2) above. The said proportion is        preferably 15%.

According to the present invention, after the operation b) of separationof the reaction mixture coming from transesterification, the phasecontaining the mixtures of fatty acid alkyl esters and the excess amountof lower alcohols or bioalcohols can be subjected to a further treatmentfor the separation of amounts ranging from 0 to 100%, preferably from 10to 100%, of alcohols or bioalcohols present after operation b) ofseparation. In practice, the said phase may not necessarily be subjectedto further separation treatments, thus keeping the whole excess quantityof lower alcohols or bioalcohols in the final product.

Alternatively, according to the uses envisaged for the product and tothe environmental conditions of use, the phase containing the mixture offatty acid alkyl esters and excess lower alcohols or bioalcohols may beadded with a further quantity of lower alcohols or bioalcohols.

From the above, it results that Bio-oil is a new biofuel obtained fromsuitable combinations of percentages of its main components—esterifiedoils and alcohols/bioalcohols.

It may be used alone or as the main ingredient of a mixture, or as abiocompatible diluent in variable percentages, in relation to thecharacteristics and use of the apparatus it is used in and the relativeenvironmental conditions of use (such as low temperatures), be it aturbogas engine, an internal combustion engine, a fuel cell, a burner,for applications in the fields of land, sea or air transportation,mechanical or electrical energy production or heating systems.

Preferably, the said lower alcohols or bioalcohols are selected fromamong methanol, ethanol, biomethanol, bioethanol and their mixtures, butthe definition of lower alcohol embraces alcohols with up to 4 carbonatoms.

Preferably, the said operation a) of transesterification is carried outwith an alkaline catalyst, according to what is already consolidated inbiodiesel production, such as sodium or potassium hydroxide or sodiummethylate. According to certain preferred embodiments of the presentinvention, this operation is carried out in three consecutive steps inwhich the said alcohols or bioalcohols and said catalyst are dosed andrecycled at every passage. This operative solution is advantageous asregards yields, because it allows making the transesterification processgo further.

In the process according to the present invention, thetransesterification takes place continuously, preferably at a maximumtemperature of 50° C. and relative pressure of 0.5 bar. As alreadynoted, recovery of the excess alcohol takes place continuously. Morespecifically, the undesired alcohol in the alkyl ester solution may beseparated by distillation. A small part thereof remains in the aqueoussolution of raw glycerine, from which it can still be recovered later.

In view of the above, if the starting material is not already a refinedoil, the integrated process proposed according to the present inventionenvisages a pre-treatment of depuration and refining of the startingoil, in order to arrive at a dried refined oil regardless of whether theprocess starts with a raw virgin oil or with used frying oils and/oranimal fats. If the starting material is already a pure, alreadyrefined, vegetable oil, the only preliminary treatment envisaged beforetransesterification is drying.

The aforesaid preliminary treatments are intended to remove extraneoussubstances (proteins, rubbers, resins, phosphates, ketones, aldehydes)which may be present either in suspension or in solution and that cannegatively influence the transesterification process or combustion. Morespecifically, in the preliminary refining of the oil, it is worthremoving any lecithin and any free fatty acids, in order to obtain astarting material with consistent characteristics.

According to a preferred embodiment of the present invention, the saidpreliminary treatment 1) of depuration of ingredient i), i.e. rawvegetable oil, includes operations of centrifugation, filtration andmucilage removal. The depuration treatment removes most of the water,impurities in suspension and the mucilage, that can generate rubbers. Inparticular, centrifugation removes the water residues, coarseimpurities, fragments of seeds, flours, carbon residues, and inhibitsthe onset of enzymatic reactions. Filtration, obtained withfilter-presses, removes all the substances in suspension not removed bycentrifugation. Demucilagination or degumming removes hydratable polarlipids (phospholipids, lipoprotids, glycolipids), resins and rubbers.

Still according to a preferred embodiment of the present invention, thepreliminary treatment 1) of depuration of the raw vegetable oil includesneutralisation and winterizing operations. With refining there isfirstly a neutralisation or de-acidification of the starting oil,enabling the removal of free fatty acids that are formed in the rawmaterial through lipase activity. This treatment is carried out byadding suitable quantities of bases, particularly sodium hydroxide, tothe raw oil. The neutralisation of the free fatty acids partly leads toforming soaps, which may incorporate considerable fractions of neutraloil.

As already noted, the integrated process according to the presentinvention may use biomethanol instead of methanol or bioethanol insteadof ethanol, in order to obtain a product with the utmost environmentalcompatibility. Mixing Bio-oil with traditional fuel in suitablepercentages according to the type of use and apparatus enablesattributing—in the same percentages—the characteristics of environmentalcompatibility of Bio-oil to the resulting mixture.

According to a further aspect thereof, the present invention alsoprovides a new biofuel or biocombustible mixture consisting of variablequantities of:

-   -   I) fatty acid alkyl esters obtainable by transesterification        starting from lipid-based vegetable or animal materials        subjected to preliminary treatments involving drying, and from        lower alcohols or bioalcohols.    -   II) lower alcohols or bioalcohols or their mixtures.

According to a first possibility, the said quantity 11) of loweralcohols or bioalcohols corresponds to the excess alcohols orbioalcohols initially found in the said transesterification operation.In this case, there is no need for operations envisaging the separationof the alcohol from the alkyl ester phase produced viatransesterification.

Depending on requirements of use, the quantity 11) of lower alcohols orbioalcohols may also be smaller than the excess alcohol or bioalcoholpresent initially in the said transesterification operation, and thismeans that, in production, there will be at least a partial separationof the alcohol contained in the alkyl ester mixture produced, such as byrapid evaporation (flash) of the alcohol, which is the lightestcomponent, from the product mixture.

Alternatively, when the mixture according to the present invention mustbe used, for example, in extreme conditions in aeronautical applicationsin order to maintain Bio-oil fluidity and to avoid separations, thequantity 11) of lower alcohols or bioalcohols may be greater than theexcess alcohol or bioalcohol initially present in the saidtransesterification operation. In which case, as noted, the finalmixture is obtained by adding further alcohol or bioalcohol after thetransesterification operation.

As will be evident from the data presented below, the process accordingto the present invention offers a product of higher quality and puritycompared to conventional processes, with lower residual glycerol contentand humidity, and yielding a glycerine by-product directly of 95-98%purity.

The specific features of the present invention, as well as itsadvantages and relative operative modalities, will be all the moreevident with reference to the detailed description presented merely forexemplificative purposes below, relating to one of its preferredembodiments. The same is illustrated in the attached drawings, wherein:

FIG. 1 shows an overall block diagram of an integrated process for theproduction of biofuels and biocombustibles according to the presentinvention;

FIG. 2 shows a block diagram of only that section of the process of FIG.1 concerning the preliminary treatment of used frying oils and animalfats;

FIG. 3 shows a block diagram of that section of the process of FIG. 1concerning the production of the mixture according to the presentinvention starting from pre-treated and dried oil.

As shown in the block diagram of FIG. 1, the process according to thepresent invention mainly consists of three sections of preliminarytreatment of the starting material. These three sections areinterconnected and can be used either together or alternatively to oneanother, depending on the type of starting material to be processed andon the characteristics required of the final product. According to thepresent invention, the oil used for the transesterification process isobtained from raw, refined or used (frying) vegetable oils and from oilsof animal origin. The raw vegetable oils are extracted fromoil-producing plant species (colza, sunflower, hemp, sorghum, coconut,soy, palm, etc.) or from algae and/or microalgae produced in aquacultureand/or in thermal bioreactors.

The third section of the process, which concerns treatment of the spentfood oils, is also shown in more detail in the block diagram of FIG. 2.

The production lines of all three sections converge in the pointindicated as “Dried refined oil”, from which the transesterificationprocess starts, with the subsequent operations of separation andrecovery of the various streams and the possible addition of loweralcohol to the Bio-oil obtained in the process.

The identity and preferred doses of the various reagents are shown inFIG. 1, while the central section of the process that carries outtransesterification, the separation of the produced streams and anymixing with additional alcohols or bioalcohols is also shown in moredetail in the block diagram of FIG. 3.

EXAMPLE

To obtain a total of 1,000 kg of Bio-oil by means of the process of thepresent invention, the preliminary treatment is carried out as follows.

Raw Vegetable Oil

If raw virgin vegetable oil is used as a starting material, with astarting quantity of 1,040 kg, the procedure is as follows:

-   -   a) pre-treatment of depuration;    -   b) pre-treatment of neutralisation with H₃PO₄ and NaOH in order        to extract soaps and dry matter;    -   c) drying treatment, which yields dried refined oil.

The dried refined oil is the nodal point (at the centre of the diagramof FIG. 1) of Bio-oil production, which is the arrival point for all thestarting materials taken into consideration.

Raw Vegetable Oil and Used Frying Oil

Starting from 1,039 kg of starting material, composed of 907 kg of rawvegetable oil mixed with 132 kg of used frying oil (UFO), or oilderiving from animal fats, the procedure is as follows:

-   -   a) for UFO and oil from animal fats, there is a pre-treatment of        centrifugation and filtration, drying and esterification with        H₂SO₄ and methanol/biomethanol or ethanol/bioethanol;    -   b) for raw vegetable oil, there is a pre-treatment of        neutralisation with H₃PO₄ and NaOH, to extract the soaps and dry        matter;    -   c) drying treatment yielding the dried refined oil.        Refined Vegetable Oil and Used Frying Oil

Starting from 1,009 kg of starting material, composed of 877 kg ofrefined vegetable oil mixed with 132 kg of used frying oil (UFO), or oilderiving from animal fats, the procedure is as follows:

-   -   a) for UFO and oil from animal fats, there is a pre-treatment of        centrifugation and filtration, drying and esterification with        H₂SO₄ and methanol/biomethanol or ethanol/bioethanol.    -   b) drying treatment yielding the dried refined oil.        Refined Vegetable Oil

Starting from 1005 kg of refined vegetable oil as starting material, theprocedure is as follows:

a) drying treatment yielding the dried refined oil.

In the production process, starting from the various combinations of theaforesaid starting materials, after the above preliminary treatments thetransesterification reaction is carried out. Then treatments ofpurification and extraction of undesired components, the addition ofcomponents necessary for particular uses (methanol and/or biomethanol,ethanol and/or bioethanol) are carried out, to finally arrive atBio-oil, as shown in the diagram of the process.

To produce 1,000 kg of Bio-oil, considering the entire process, thefollowing chemicals and relative quantities are used:

CHEMICALS MIN (kg) MAX (kg) Biomethanol 0*  450 Methanol 0*  450Bioethanol 0*  450 Ethanol 0*  450 Sodium methylate 5.0 10.5 Citric acid0.5 1.5 96% sulphuric acid 0.5 1.7 36% hydrogen chloride 13.0  15.5 80%phosphoric acid 1.5 3.00 50% caustic soda 10.5  13.7 *The four productsare combined according to the optimal percentages necessary for the typeof starting material and for the type of Bio-oil to be produced. Forminimum environmental impact, the process will use biomethanol andbioethanol in suitable proportions.

Table 1 below reports some characteristics of biodiesel for motorvehicles according to UNI EN 14 424 specifications, in comparison withthe Bio-oil produced according to the procedure of the presentinvention.

TABLE 1 COMPARISON OF BIODIESEL AND BIO-OIL PROPERTIES BIODIESEL BIO-OILLimits Limits Properties Unit Min Max Min Max Test method Ester content% (m/m) 96.5 98.5 EN 14103 Volumetric mass at 15° C. kg/m³ 860 900 860900 EN ISO 3675 EN ISO 12185 Viscosity at 40° C. mm²/s 3.50 5.00 1.504.00 EN ISO 3104 Flash-point ° C. 120 — >110 — prEN ISO 3679 Sulphurcontent mg/kg — 10.0 — ≦10.0 EN ISO 20846 EN ISO 20884 Carboniousresidue (on 10% residue of distillation) % (m/m) — 0.30 — ≦0.30 EN ISO10370 Ketane number 51.0 EN ISO 5165 Sulphated ash content % (m/m) —0.02 ISO 3987 Water content mg/kg — 500 — ≦500 EN ISO 12937 Total solidcontaminants mg/kg — 24 — ≦20 EN 12662 Corrosion on copper lamina (3 hat 50° C.) Classification class 1 class 1 EN ISO 2160 Oxidationstability, 110° C. hours 6.0 — 6.0 — EN 14112 Acidity value mg KOH/g0.50 EN 14104 Iodine value g iodine/100 g 120 110 EN 14111 Methyl esterof linolenic acid % (m/m) 12.0 11.0 EN 14103 Polyunsaturated methylesters (≧4 double bonds) % (m/m) 1 1 Methanol content % (m/m) 0.20 45.0EN 14110 Biomethanol content % (m/m) 45.0 Ethanol content % (m/m) 45.0Bioethanol content % (m/m) 45.0 Monoglyceride content % (m/m) 0.80 0.70EN 14105 Diglyceride content % (m/m) 0.20 0.19 EN 14105 Triglyceridecontent % (m/m) 0.20 0.20 EN 14105 Free glycerol % (m/m) 0.02 0.02 EN14105 EN 14106 Monoglyceride content % (m/m) 0.80 0.80 EN 14105Diglyceride content % (m/m) 0.20 0.20 EN 14105 Triglyceride content %(m/m) 0.20 0.20 EN 14105 Free glycerol % (m/m) 0.02 0.02 EN 14105 EN14106 Total glycerol % (m/m) 0.25 0.23 EN 14105 Group I metals (Na + K)mg/kg 5.0 5.0 EN 14108 EN 14109 Group II metals (Ca + Mg) mg/kg 5.0 5.0prEN 14538 Phosphorous content mg/kg 10.0 10.0 EN 14107

From the above data, as well as from what is already known in the fieldof combustibles/fuels obtained from biomasses, it appears that themixtures according to the present invention (Bio-oil) represent abiofuel of very low environmental impact. Even when mixed with fossildiesel fuel, it does not lose its biocompatibility, but the mixtureitself enhances its own positive characteristics as a function of thepercentage of Bio-oil used.

The direct and indirect advantages of the biofuel include safety of use,due to its high flash-point of over 110° C., and its highbiodegradability in soil or water, which is maintained in thecorresponding percentage even when mixed with fossil diesel fuel.

Moreover, the biofuel mixture according to the present invention allowsreducing nearly all levels of emission, also with respect to biodiesel,which already presents considerable advantages in this regard. Inparticular, carbon monoxide and non-combusted residues are lower becauseusing alcohol lowers the combustion temperature, and the presence ofoxygen in the alkyl ester molecule contributes to a better combustion.

The carbon dioxide produced by Bio-oil, owing to its vegetable origin,is compensated by the carbon dioxide absorbed by the plants grown forthe production of the starting oil. As regards this advantageous effect,there is, for example, an average reduction of 2.5 tonnes of CO₂ emittedfor each tonne of fossil diesel replaced.

As with other biofuels, the vegetable origin of Bio-oil guarantees theabsence of heavy metals and, since it does not contain sulphur, itreduces pollutants, does not contribute to acid rain and increases theefficiency and duration of catalysts of transport vehicles and ofindustrial plants. There are also no aromatic polycyclic hydrocarbons,which are highly cancerogenous.

Moreover, there is a considerable decrease in mutagenicity values ofPM10 fine particulate emissions, especially in the most harmful part,the carbonious one. The carbonious part is the one that is absorbed themost during respiration and is difficult to block in catalysts inindustrial plants and transport vehicles.

In a different and more advantageous manner with respect to biodiesel,Bio-oil associates the known detergent and lubricant properties of alkylester combustibles (biodiesel) and the slightly corrosive properties ofalcohols, thereby enhancing the safety, reliability and efficiency ofsystems. The detergent property of Bio-oil, which means a considerablereduction of industrial plant dirtying, leads to less frequentmaintenance work for some components as well as greater safety andreliability owing to better system functioning.

In particular, those critical components of the apparatus that areparticularly critical for efficiency are kept clean: namely, the areaswhere chemical reactions take place and where there is oxidation linkedto energy production, as in the case of fuel cells, turbines, internalcombustion engines and burners. The same beneficial detergent, lubricantand slightly corrosive effect is obtained for apparatus components wherethe biofuel passes through or remains in, such as nozzles, conduits,injectors, piping, tanks etc.

In short, Bio-oil has the following advantageous characteristics:

-   -   a high flash-point of over 110° C.    -   high biodegradability in soil or water, of over 99.5% after 20        years    -   an average reduction of CO₂ emission on overall balance    -   a reduction of fine particulate (PM10) of 58%; a reduction of        76% of the carbonious part of fine particulate (soot) and a        resulting reduction of the mutagenicity values for the        particulate.    -   greater oxygen content, of about 11% with respect to fossil        diesel fuel.    -   no aromatic polycyclic hydrocarbons, heavy metals or sulphur.    -   a 58% abatement of carbon monoxide emissions at high loads.    -   a decrease in aromatic compounds of up to 68%.    -   a detergent and lubricant action on system components.

The present invention has been disclosed with reference to some specificembodiments thereof, but it is to be understood that variations ormodifications can be brought by persons skilled in the art withoutdeparting from the scope of the appended claims.

The invention claimed is:
 1. A process for the production ofbiocombustible and biofuel mixtures suitable for different conditions ofuse, comprising: a) pre-treating lipid-based vegetable or animalmaterials, wherein the lipid-based vegetable or animal materialscomprises used food oil and/or animal fats and at least one of rawvegetable oil and refined vegetable oil, and wherein the pre-treatmentcomprises: i) if using the raw vegetable oil, subjecting the rawvegetable oil to a preliminary depuration and refining treatment toremove impurities and to neutralize and winterize the raw vegetable oil,and thereafter drying of the refined oil thus obtained; ii) if using therefined vegetable oil, subjecting the refined vegetable oil topreliminary drying; and iii) subjecting the used food oil and/or animalfats to a preliminary depuration treatment, drying and an esterificationof the free fatty acids contained therein by addition of lower alcoholsor bioalcohols to obtain an esterified product of the used food oiland/or animal fats; b) mixing the esterified product of the used foodoil and/or animal fats in a proportion of not more than 20% with driedrefined oil obtained from the steps i) and/or ii); c) producing mixturesof fatty acid alkyl esters and glycerine by transesterification of theproduct of step b) with lower alcohols of bioalchohols in excess; and d)separating the mixtures obtained from the step c) of transesterificationinto a phase containing raw glycerine and a phase containing themixtures of fatty acid alkyl esters and the excess amount of loweralcohols or bioalcohols; wherein the final biocombustible and biofuelmixture contains mixtures of fatty acid alkyl esters and alcohols and/orbioalcohols, wherein the alcohols or bioalcohols are present in acalibrated quantity.
 2. A process according to claim 1, wherein, afterthe step d) of separation, the phase containing said mixtures of fattyacid alkyl esters and the excess amount of lower alcohols or bioalcoholsis subjected to a further separation treatment to remove a portion ofthe alcohols or bioalcohols present after the step d) of separation. 3.A process according to claim 1, wherein, after the step d) ofseparation, the phase containing said mixtures of fatty acid alkylesters and said excess amount of lower alcohols or bioalcohols is notsubjected to further separation treatments, and the whole excessquantity of lower alcohols or bioalcohols is kept in the final product.4. A process according to claim 1, wherein, after the step d) ofseparation, an additional amount of lower alcohols or bioalcohols isadded to the phase containing the mixtures of fatty acid alkyl estersand the excess lower alcohols or bioalcohols.
 5. A process according toclaim 1, wherein the lower alcohols or bioalcohols are selected from thegroup consisting of methanol, ethanol, biomethanol, bioethanol and theirmixtures.
 6. A process according to claim 1, wherein the step c) oftransesterification is carried out with an alkaline catalyst.
 7. Aprocess according to claim 6, wherein the step c) of transesterificationis carried out in three consecutive stages in which the alcohols orbioalcohols and the catalyst are dosed and recycled at every stage.
 8. Aprocess according to claim 1, wherein the preliminary treatment 1) ofdepuration of raw vegetable oil includes operations of centrifugation,filtration and demucilagination.